JPH0593084A - Foaming and curing of resin and plastic material with cyclodextrin composite - Google Patents

Abstract

PURPOSE: To provide a plastic expanding method good in storage stability and having no dusting and explosion danger and avoided from a problem of toxitity and combustibility.

CONSTITUTION: 1-15 pts.wt. of a composite (B) obtained by compounding 1-30 pts.wt. of a blowing foaming agent (e.g.; water, propylene glycol, dipropylene glycol) B₂ with 100 pts.wt. of cyclodextrin (e.g.; betacyclodextrin) B₁ is compounded with 100 pts.wt. of a plastic material (e.g.; polystyrene, polyvinyl chlororide) (A) and the plastic material (A) is expanded by the foaming agent in a state fluidized by heating.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foaming agent, and more particularly to a chemical foaming agent which releases gas upon heating to expand a fluidized plastic material.

[0002]

BACKGROUND OF THE INVENTION A foaming agent, which is sometimes called a foaming agent, is a substance that forms a spongy structure in a fluidized plastic or rubber composition. Conventional blowing agents include fluorocarbons, nitrogen gas, hydrazine derivatives,
There are trihydrazide triazines, 5-phenyltetrazole, p-toluenesulfonyl semicarbazide, modified azodicarbonamides, and azodicarbonamides. Chemical blowing agents are a type of blowing agent that are solid or liquid at room temperature and release gas upon heating.
The well-known chemical foaming agent is sold by Uniroyal under the trademark Serogen.

The hard plastic or rubber composition having a spongy structure obtained by using a foaming agent is generally referred to as structural foam, spongy polymer, spongy plastic, expanded plastic, and expanded plastic. Probably one of the first synthetic spongy plastics was sponge rubber. For clarity, materials expanded with blowing agents are generally referred to as plastic materials unless a particular type of plastic material is a problem, such as sealants, adhesives or ethylene vinyl acetate (EVA). I will call it. Foaming agents can be used for various daily necessities, such as furniture and building materials such as upholstery materials, floors, wall or ceiling tiles, picture and mirror frames, drawer shelves, ornaments, planters, doors, decorative or finishing items, lamps , Appliance parts, wine racks, chaise lounges and chair frames, shutters, and bed frames. Foaming agents are also used in the manufacture of automotive parts such as battery cases, fan covers, doors for small items, duct structures for air conditioners, upholstery materials, cushioning materials, bucket seat frames, and automotive sealants. .. Foaming agents are also used in plastic materials for making marine components such as boat ladders, center deck of sailboats, buoys and floats, modular hulls, lobster pots. Furthermore, foaming agents include pallets, trays, soda cases, tool boxes, drums and various containers,
Manufactures ice buckets, bird baths, croquet wood and balls, children's toys, recreational vehicle parts, bowling pins, shuffleboard equipment, sports equipment such as hockey sticks and baseball bats, and footwear. Used for plastic material. Further, foaming agents are used with adhesive plastic materials in hot melt adhesives. The foaming agent is also used as a food packaging material to be attached to the outside of livestock after slaughtering the livestock and before wholesale. Such products are sometimes called "bone wraps".

Generally, the chemical blowing agent is mixed with a solid plastic material and then the mixture is heated under pressure. The heating causes the plastic material to fluidize and the foaming agent releases gas. This gas forms bubbles or microchambers in the fluid plastic material. The mixture is placed under pressure in a mold where the gas expands and the fluid plastic material expands. The microchamber structure remains intact after solidification. Since the gas release temperature varies depending on the type of foaming agent, the foaming agent is selected according to the processing conditions, the plastic material, and the desired bubble size.

[0005]

[Problems to be Solved by the Invention] Chemical blowing agents include
It has the advantage over gaseous blowing agents that it can be added to the solid plastic material before heating. Gaseous blowing agents such as nitrogen and some fluorocarbons must be injected into the fluidized plastic material. In hot melt adhesives, gas is mixed into the adhesive before the end of the nozzle. The use of fluorocarbons as blowing agents has come under close scrutiny because their impact on the Earth's ozone layer has become a problem. Other conventional foaming agents have handling, toxicity and flammability issues. Handling problems include storage stability, dust, and risk of explosion.

[0006]

It has now been found that a complex of cyclodextrin and a foaming agent acts as a foaming agent in a fluidized plastic material. Cyclodextrins have been found to stabilize foaming agents. It was also found that certain compounds, which have never been used as foaming agents, can be used as foaming agents.

The present invention comprises the steps of forming a mixture of a plastic material and a complex of a blowing agent and cyclodextrin, and heating the mixture to fluidize the plastic material and release gas into the composite. And a method of expanding a plastic material. The gas forms bubbles in the fluidized plastic material.

First, a complex of cyclodextrin and a foaming agent is formed, and the complex is mixed with a plastic material.

The step of heating the mixture is carried out by applying heat to the mixture as is generally done by conventional extrusion or blow molding methods, or by the heat of exothermic reaction normally carried out in the case of polyurethanes.

The inflatable plastic composition produced according to the present invention comprises a plastic material and a complex of cyclodextrin and a blowing agent. Inflatable plastic compositions are used, for example, to make foam structures and certain adhesives.

The expanded structure formed according to the present invention is
It is prepared by heating and molding a mixture of a structural plastic material and a complex of a blowing agent and cyclodextrin.

The adhesive and / or sealant composition produced according to the present invention comprises an adhesive and / or sealant plastic material and a complex of a foaming agent and cyclodextrin.

Cyclodextrin, also called "Schalzinger dextrin", cycloamylose, cyclomaltose and cycloglucan, is an oligomer of anhydroglucose which is linked together by alpha 1,4 bonds to form cyclic compounds. 6-membered ring is alpha cyclodextrin, 7-membered ring is beta cyclodextrin,
And the 8-membered ring is called gamma cyclodextrin.
These 6, 7 and 8 membered rings are also referred to as cyclomaltohexaose, cyclomaltoheptaose and cyclomaltooctaose, respectively.

Cyclodextrin is usually obtained by treating a starch slurry with an enzyme or an acid to give a gelatinized, liquefied slurry having a DE between 1 and 5. The gelatinized, liquefied starch slurry is then treated with cyclodextrin glycosyl transferase (CGT) to a pH suitable for the selected CGT,
Treat at temperature and time. The enzyme CGT is Bacillus
Cerance , B. Magatherium , B. Circulance ,
B. Stearothermophilus, and Bacillus sp.
(Alkalophilic), obtained from other microorganisms. Then, the gelatinized and liquefied starch slurry is treated with CGT to separate and purify the digested product, whereby cyclodextrin is obtained.

One of the commercially important characteristics of cyclodextrins is their ability to act as clathrates or hosts for other commercially available compounds. Cyclodextrins physically have a donut shape. As a result, cyclodextrins can act as clathrates for substances that have a geometric outer dimension that corresponds to the diameter of the cyclodextrin space. The cyclodextrin is often modified like a hydroxypropyl cyclodextrin by adding a side chain to the donut-shaped exterior.
The term "cyclodextrin" as used herein and in the claims means not only cyclodextrin itself, but also modified cyclodextrin and branched cyclodextrins.

As used herein and in the claims, the term "complex" or the expression "complex of cyclodextrin and a blowing agent" is such that cyclodextrin acts as a host on the blowing agent. It means not only a composition of cyclodextrin and a foaming agent, but also a composition in which the foaming agent is bound to the outside of cyclodextrin by a weak binding force.

As a method of forming a complex of cyclodextrin and a foaming agent, there is a method of dissolving cyclodextrin in water together with the foaming agent and collecting the resulting precipitate.

Another method is to load a ball mill with cyclodextrin and a foaming agent and grind the mixture in the hole mill for a certain period of time to form a complex between the cyclodextrin and the foaming agent. Other known methods for forming a complex between cyclodextrin and a foaming agent include kneading, lyophilization, and co-milling. Good results have been obtained with co-milling using a mortar and pestle.

Preference is given to using alpha, beta or gamma cyclodextrins for the present invention. Beta-cyclodextrin is preferred as it is commercially available. The conjugate prepared from the combination of all three cyclodextrins releases the foaming agent at different rates. It is considered that this is partly because the binding strength with the foaming agent differs depending on the cyclodextrin.

Suitable blowing agents include water, liquids such as propylene glycol, dipropylene glycol, tripropylene glycol, cyclohexylamine, dicyclohexylamine and ethylene glycol, and benzoyl peroxide and other peroxides which are difficult to process. There is a solid like a thing. It was surprising and unexpected that water, propylene glycol, dipropylene glycol, tripropylene glycol and ethylene glycol were effective as foaming agents. So far, water, propylene glycol, dipropylene glycol, tripropylene glycol and ethylene glycol have not been used as foaming agents because of their poor dispersibility in plastic materials. Solids such as benzoyl peroxide are
Processing is difficult due to the low decomposition temperature. Water and propylene glycol are considered safe and non-toxic to humans. Many conventional foaming agents are toxic to humans. The use of such a non-toxic foaming agent in the workplace brings unprecedented safety to the workplace. The use temperature of the foaming agent can be changed by using a combination of two or more foaming agents such as water and propylene glycol, or by using the same foaming agent with different cyclodextrins. ..

Further, according to the present invention, a hydrazine derivative which forms a complex with cyclodextrin, trihydrazide triazine, 5-phenyltetrazole, p-toluenesulfonyl semicarbazide, modified azodicarbonamide, and azodicarbonamide are used as a foaming agent. can do. Dust is reduced by complexing conventional foaming agent with cyclodextrin,
The composition stabilizes.

The amount of the foaming agent complexed with cyclodextrin is about 1 to about 30 parts by weight (phc) based on 100 parts by weight of cyclodextrin. More preferably about 3 to about
Complexed with cyclodextrin at 15 phc, most preferably about 5 to about 7 phc of the foaming agent.

When forming the complex between the cyclodextrin and the foaming agent, an excess amount of the foaming agent is used to form the complex.

Cyclodextrin obtained from commercial production of cyclodextrin has been found to be a suitable source of the complex of cyclodextrin and water. Cyclodextrins obtained from commercial production processes are generally about 10 to about
Contains 12 phc of water. When this cyclodextrin is used in an adhesive composition, sufficient gas is obtained by heating, so that commercially available cyclodextrin complexed with about 10 to about 12 phc of water acts as a foaming agent.

It has been found that, in general, the smaller the particle size of the composite, the more uniform the cell size. Good results have been obtained with a complex of cyclodextrin and foaming agent with a particle size that can pass through 200 mesh.

Suitable plastic materials include polymers such as polystyrene, polyvinyl chloride, polyethylene, polyurethane, polyphenols, polypropylene, polyisoprene (rubber), polybutadiene, as well as acrylonitrile-butadiene-styrene, styrene-isoprene, ethylene-. Butylene, styrene-butadiene rubber,
And copolymers such as ethylene vinyl acetate.

The foamed structure has a structure-like plastic material and about 1 to 100 parts by weight of the plastic material.
Produced by forming a mixture of about 15 parts by weight (php) cyclodextrin and water complex, heating the mixture to expand the plastic material, and allowing the expanded mixture to cool. More specifically, the foamed structure is made by conventional methods by placing about 1 to about 10 php of cyclodextrin and water complex together with the structural plastic material into the extruder hopper. The composite of the present invention is mixed with a plastic material, then the mixture is subjected to conventional molding steps, the mixture is heated and the fluidized plastic material is filled into a mold. Such molding operations are conventional. In the molding process, the conventional chemical blowing agent is replaced by the composite of the present invention.

Examples of structural plastic materials are polystyrene, polyethylene, polyurethane, polyisoprene, epoxy resins, and polyvinyl chloride.

The adhesive and / or sealant composition produced in accordance with the present invention comprises an adhesive plastic material and a complex of about 1 to about 30 php cyclodextrin and water.

Examples of adhesive plastic materials are ethylene vinyl acetate (EVA), acrylonitrile-butadiene-styrene and styrene-isoprene.
Good results have been obtained by using the conjugates of the invention and EVA.

The expandable plastic composition according to the present invention comprises about 1 to about 15 php of a foaming agent / cyclodextrin complex, and a plastic material. The expandable plastic composition is prepared by mixing the composite with a plastic material. A typical adhesive produced according to the present invention has the following composition. Parts by weight EVA 25-50 modified resin 25-60 wax 0-30 total amount of adhesive plastic material 100 antioxidant 0.05-0.5 php filler 0-100 php foaming agent-cyclodextrin complex 1-10 php The bookbinding adhesive produced according to the present invention has the following composition. Parts by weight EVA 35-45 modified resin 20-30 plasticizer 20-30 wax 10-20 total amount of adhesive plastic material 100 antioxidant 0.05-0.25 php foaming agent-cyclodextrin complex 1-10 php Antifungal agent (optional) 1-10 php Preferably, the blowing agent-cyclodextrin complex is a water-cyclodextrin complex and comprises about 8 to about 15 phc water. More preferably, the amount of composite used in the bookbinding adhesive is from about 3 to about 7 phc and contains from about 10 to about 15 phc water. When a bactericidal agent or antifungal agent is complexed with cyclodextrin and compounded in an adhesive to be used, it helps prevent deterioration. Water acts as a foaming agent and helps release fungicides or fungicides.

The bookbinding adhesive is produced by mixing all the components in a conventional manner.

The temperature of use of such adhesives is about 120 to about 20.
It is 5 ° C.

The use of the cyclodextrin / water complex offers several advantages over the prior art use of liquid nitrogen. Current machines for applying hot melts for bookbinding require specialized machinery for compounding liquid nitrogen. A much wider range of devices can be used with the cyclodextrin-water complex according to the invention. In addition, there is more open time, more surface contact, and less adhesive used to cover the same area.

The paper box and case sealing adhesive produced according to the present invention has the following composition: Parts by weight EVA 40 modified resin 40 wax 20 total amount of adhesive plastic material 100 antioxidant 0.01 php foaming agent-cyclodextrin complex 1-10 php Preferably, foaming agent-cyclodextrin complex is propylene glycol- It is a cyclodextrin complex and has about 8 to about 15 phc propylene glycol.
Preferably, the propylene glycol content is about 10 to about
Use about 3 to about 7 php of complex which is 13 phc.

Paper box and case sealing adhesives are prepared by mixing all the ingredients in a conventional manner.

The temperature of use of such adhesives is about 175 to about 20.
It is 5 ° C.

The carpet backing adhesive produced according to the present invention has the following composition. Parts by weight EVA 25-50 modified resin 25-60 wax 0-30 total amount of adhesive plastic material 100 antioxidant 0.05-0.5 php filler 0-100 php foaming agent-cyclodextrin complex 1-10 php The blowing agent-cyclodextrin complex used in this carpet backing adhesive is cyclodextrin and about 8 to about 15 phc water, propylene glycol, or a combination of water and propylene glycol, or water, propylene glycol. And a combination of hydrazine derivatives.

Further, such a carpet backing adhesive comprises a composite of cyclodextrin and a fungicide at about 1 p.
It is preferably included in an amount up to hp. Suitable fungicides include
There are diiodomethyl-p-tolylsulfone, phenol and butylhydroxytoluene, but diiodomethyl-p-tolylsulfone is preferred and its release is caused by the water released by the cyclodextrin.

The carpet backing adhesive is prepared by mixing all the ingredients in a conventional manner.

The operating temperature of the carpet backing adhesive is from about 149 ° C to about 177 ° C.

A small amount of an enzyme called amylase added to the expandable plastic material according to the present invention acts as a catalyst by heating, and enhances the rate at which the blowing agent is released from cyclodextrin. In order for the amylase to act as a catalyst, a small amount of water must be present in the plastic composition. It is believed that the amylase uses water to destroy the cyclodextrin, thereby promoting the release of the foaming agent.

Of course, other compounds can be added to the plasticizer material containing the foaming agent of the present invention, including fungicides, fungicides and perfumes.

These and other features of the invention are described in further detail by the examples provided below.

[0045]

EXAMPLE 1 This example illustrates a hot melt adhesive, particularly a bookbinding adhesive, according to the present invention. Binding material parts by weight EVA-507 45 Stavelite resin 25 Pentaline H 20 Microcrystalline wax 10 Total binding plastic material 100 This adhesive plasticizer material contains 0.1 php antioxidant and 10
The php water-beta cyclodextrin complex was added.
This complex contains 7.5 grams of beta-cyclodextrin and 2.5 grams of water. The cyclodextrin and water were complexed by mixing excess water with cyclodextrin. After mixing the adhesive plastics material with the antioxidant and the water-beta cyclodextrin complex, heating the mixture to 100 ° C causes water to transform from the liquid phase to the vapor phase at this temperature, thereby expanding the adhesive. Let The volume expansion coefficient of the adhesive was about 100%.

EVA-507 is an ethylene-vinyl acetate copolymer commercially available from Union Carbide. Stavelite resin is a hydrogenated resin and plasticizer containing diethylene glycol ester of hydrogenated resin, obtained from Hercules Powder Company. Pentaline H
Is a synthetic resin obtained from Hercules Powder Company. Microcrystalline wax is a commercially available wax obtained from Petrolite, Inc., Tulsa, OK. The antioxidant is Irganox 1010 obtained from Ciba-Geigy. Beta cyclodextrin is
Betacyclodextrin obtained from American Maze-Products, Inc. of Hammond, Indiana. The water is normal tap water.

It is surprising and unexpected that the complex of cyclodextrin and water in this formulation functioned as a foaming agent, as water itself does not function as a foaming agent in the binding adhesive. there were.

[0048]

Example 2 This example illustrates a method for producing an adhesive for paper boxes and cases according to the present invention. The following adhesive composition was prepared. Material parts by weight EVA-305 40 CKM-2400 15 Picolite A-115 12.5 Super Statak 12.5 Polywax 1000 10 Castor wax 10 Total adhesive plastic material 100 0.1 php antioxidant in this adhesive plasticizer material And 10
The propylene glycol-beta cyclodextrin complex of php was mixed. This complex contains 1 mol of beta cyclodextrin and 2 mol of propylene glycol. A complex of cyclodextrin and propylene glycol was prepared by mixing an excess of propylene glycol with beta cyclodextrin.

The mixture of adhesive material, antioxidant and propylene glycol-beta cyclodextrin complex was heated. Propylene glycol converted from the liquid phase to the gas phase, thereby expanding the adhesive composition. The adhesive composition contains propylene glycol, which is a foaming agent,
It expanded about 100% in volume.

EVA-305 is an ethylene-vinyl acetate copolymer commercially available from Union Carbide. CKM-2400 was obtained from Union Carbide. Picolite A-115 is a thermoplastic terpene resin obtained from Hercules. SuperStatac was obtained from Reihold Chemical Company. Poly wax 1
000 was obtained from Valeco and castor wax was obtained from Universal Pleasure Bachems. The antioxidant is Irganox 1010. Beta cyclodextrin is a beta cyclodextrin obtained from American Maze-Products, Inc. of Hammond, Indiana. Propylene glycol is a commercial product obtained from Dow Chemical Company.

Since propylene glycol itself does not function as a foaming agent, it was surprising and unexpected that the complex of cyclodextrin and propylene glycol in this formulation functioned as a foaming agent.

[0052]

EXAMPLE 3 This example illustrates the method of making the carpet backing adhesive of the present invention. The following adhesive composition was prepared. Material parts by weight EVA 50 Modified resin 40 Wax 10 Total of adhesive plastic material 100 Antifungal agent (optionally used) 1-10 php 0.1 php antioxidant, about 20 in this adhesive plasticizer material
The php filler and 5 php water-beta cyclodextrin complex were added along with 5 parts propylene glycol-beta cyclodextrin. The complex of this foaming agent and cyclodextrin was prepared as in Examples 1 and 2 above.
Was prepared according to. Both the foaming agent and cyclodextrin complex were simultaneously mixed with the adhesive composition in the same manner as in Examples 1 and 2.

Heating the mixture of adhesive composition and both blowing agents to about 195 ° C. caused the adhesive mixture to swell.

EVA is an ethylene-vinyl acetate copolymer. The modified resin is a commercially available wood rosin. Waxes are commercially available waxes commonly used in carpet backing adhesives. Antioxidant is Irganox 1010
And the filler is normal calcium carbonate.

[0055]

EXAMPLE 4 This example illustrates a method of making the pressure sensitive adhesive of the present invention.

The following adhesive composition was prepared. Material parts by weight EVA 501 15 EVA 605 30 Stavelite ester 10 37 Abitol 18 Total plastic adhesive 100 To this adhesive plasticizer material, 0.1 php of antioxidant Irganox 1010, 5 php of water and beta cyclodextrin complex, and 5 php cyclohexylamine and beta cyclodextrin were added. This water-beta-cyclodextrin complex contains 12.8 phc of water. A complex of beta cyclodextrin and cyclohexylamine, a volatile corrosion inhibitor, contains 8 phc of cyclohexylamine complexed with cyclodextrin.
Preparation of the composite and mixing of the adhesive composition were carried out as in Example 1.

The released moisture becomes a "trigger" mechanism,
This partially releases the complexed cyclohexylamine and equilibrates with the moisture released from the water-cyclodextrin complex. With such a mechanism, an effect of preventing corrosion on the metal surface can be obtained. Cyclodextrin stabilizes cyclohexylamine in the heating step by complexing with cyclohexylamine. Uncomplexed cyclohexylamine is unstable during the heating process of the adhesive. EVA501 and EVA605 are commercial ethylene-vinyl acetate copolymers obtained from Union Carbide. Stay Bright Ester 10
And Abitol was obtained from Hercules. The operating temperature of this adhesive is about 149-163 ° C.

[0058]

EXAMPLE 5 This example illustrates a method of making an inflatable and curable sealant according to the present invention.

A. - hot melt base material part Kraton FC1901x 100 (available from Shell) Regarurezu 1018 270 (available from Hercules) ene DEX 155 50 (available from Hercules) Irganox 1010 1 (available from Ciba-Geigy) B. -Plasticizer Overbased calcium sulphonate 10 (available from Witco) Beta-cyclodextrin: cyclohexylamine 2 complex (2: 1 molar ratio) Aluminum paste (available from Sun Oil 1 50:50 aluminum in Sunpearl 2280) ) Betacyclodextrin (10-13% H ₂ O) 2 Equivalent hot melt base and plasticizer are mixed, cooled,
It was mounted on a cold rolled steel sheet or a galvanized cold rolled steel sheet. Place these sheets in a furnace at 200 ° C
Heated for 15 minutes. The material expanded on the plate both vertically and horizontally, doubling the volume.

[0060]

Example 6 50 parts of the hot melt base of Example 5 above
Part of overbased calcium sulfonate.
The overbased calcium sulfonate is heated to evaporate the water before mixing with the hot melt base. The mixture was placed on a cold rolled steel sheet and a galvanized cold rolled steel sheet and heated in a furnace at 200 ° C for 15 minutes. The mixture melted on heating and spread over the plate without expanding.

[0061]

Example 7 A mixture was prepared in the same manner as in Example 6 above, except that water was not evaporated from the overbased calcium sulfonate before mixing, and the cold-rolled steel sheet and the galvanized cold-rolled steel sheet were prepared. It was placed on top and heated in a furnace at 200 ° C. The mixture of this example was simply cured as it was. The release of water accelerated the cure as evidenced by the lack of flowability and deformation of the material placed on the sheet.

[0062]

Example 8 A mixture was prepared in the same manner as in Example 5 above, except that the mixture was not cooled, placed on a cold-rolled steel sheet and a galvanized cold-rolled steel sheet, and heated at 200 ° C. in a furnace. Heated at. The material expanded in volume about twice. The blowing agent, water, was in the cyclodextrin and was released on heating along with the vapor phase corrosion inhibitor cyclohexylamine. The water is retained in the cyclodextrin and is not used for curing until sufficient heat is applied to cause its release.

[0063]

Example 9 A conventional sealant having the following composition was prepared. Materials - (available from Shell) Formula A part Kraton RD6501 100 Regarurezu 1018 270 (available from Hercules) ene DEX 155 50 (available from Hercules) Irganox 1010 1 (available from Ciba-Geigy) was mixed with this material, cold It was placed on hot rolled steel sheet and galvanized cold rolled steel sheet and heated in a furnace at 200 ° C. for 15 minutes. The mixture was melted by heating and spread on the plate.

[0064]

Example 10 This example uses Formulation A to prepare a sealant according to the present invention. Material Part Blend A 10 beta cyclodextrin (10-13% water) 2 Mix these materials and place them on a cold rolled steel sheet or a galvanized cold rolled steel sheet at 200 ° C. in a furnace.
Heated for 15 minutes. The mixture swelled, but not 100% of its original volume.

[0065]

Example 11 This example illustrates the use of another chemical blowing agent complexed with cyclodextrin. Material Part Blend A 10 beta cyclodextrin dibutyltin 2 dilaurate ester complex (24% chemical blowing agent) beta cyclodextrin (10 to 13% water) 2 After mixing, cold rolled steel sheet or zinc plating of these materials Cold rolled steel sheet and placed in a furnace at 200 ° C
Heated for 15 minutes. The mixture also expanded on heating to about 100% of its original volume.

[0066]

Example 12 This example illustrates the use of a complex of beta-cyclodextrin and benzoyl peroxide which acts as both a blowing agent and a curing agent for thermoplastics. The following compositions were prepared.

[0067] amount of material A. Fusabond C-D198 10 g (obtained from DuPont) Betacyclodextrin 1 g complex of benzoyl peroxide (10% benzoyl peroxide) B.I. Fusabond C-D198 10 g C.I. Fusabond C-D198 10 g beta cyclodextrin (10% water) 1 g D.I. Fusabond C-D198 10 g Benzoyl peroxide 0.1 g Each composition was mixed with heating and extruded into a sheet of uniform thickness between the liquids. A piece of equal length and weight was cut from this sheet, placed in an oven and heated at 200 ° C.

It was confirmed by the formation of bubbles that the uncomplexed benzoyl peroxide decomposed during mixing.

This was not confirmed when the complex of benzoyl peroxide and beta cyclodextrin was mixed under the same conditions. Both compositions had equal amounts of benzoyl peroxide. In the complexed state, benzoyl peroxide was stable upon mixing. Further, it was difficult to uniformly disperse benzoyl peroxide which was not complexed during mixing. The beta cyclodextrin-benzoyl peroxide complex was easily mixed when the composition was mixed and dispersed evenly.

After heating, the difference was very significant. Composition D, which contains uncomplexed benzoyl peroxide,
It set very quickly and did not spread widely. The bubbles in the cured composition were non-uniform in size and dispersion.

Composition A, which contained the beta-cyclodextrin complex of benzoyl peroxide, also cured rapidly and did not spread widely. Effervescence and hardening occurred simultaneously. This composition lifted higher than sample D with uncomplexed benzoyl peroxide. The bubbles of composition A were uniform in size and dispersion.

Composition C diffused better than any other composition. The water released from the cyclodextrin formed bubbles of uniform size and distribution. The water released acted as a conventional foaming agent, but there was no hardener to cure the composition and retard diffusion.

Composition B diffused more laterally than Compositions A and D, but not as much as Composition C. There was no diffusion retarding effector or diffusion enhancing foaming agent.

The best results were obtained with composition A containing a complex of benzoyl peroxide and beta cyclodextrin. Benzoyl peroxide was stabilized, released upon heating and acted as both a hardener and a foaming agent. The complex was easily mixed and dispersed in the composition.

Of course, all variations and modifications of the preferred embodiments of the invention described herein are included in the invention without departing from the spirit and scope of the invention.

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[Procedure amendment]

[Submission date] July 16, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foaming agent, and more particularly to a chemical foaming agent which releases gas upon heating to expand a fluidized plastic material.

[0002]

BACKGROUND OF THE INVENTION A foaming agent, which is sometimes called a foaming agent, is a substance that forms a spongy structure in a fluidized plastic or rubber composition. Conventional blowing agents include fluorocarbons, nitrogen gas, hydrazine derivatives,
There are trihydrazide triazines, 5-phenyltetrazole, p-toluenesulfonyl semicarbazide, modified azodicarbonamides, and azodicarbonamides. Chemical blowing agents are a type of blowing agent that are solid or liquid at room temperature and release gas upon heating.
The well-known chemical foaming agent is sold by Uniroyal under the trademark Serogen.

The hard plastic or rubber composition having a spongy structure obtained by using a foaming agent is generally referred to as structural foam, spongy polymer, spongy plastic, expanded plastic, and expanded plastic. Probably one of the first synthetic spongy plastics was sponge rubber. For clarity, materials expanded with blowing agents are generally referred to as plastic materials unless a particular type of plastic material is a problem, such as sealants, adhesives or ethylene vinyl acetate (EVA). I will call it. Foaming agents can be used for various daily necessities, such as furniture and building materials such as upholstery materials, floors, wall or ceiling tiles, picture and mirror frames, drawer shelves, ornaments, planters, doors, decorative or finishing items, lamps , Appliance parts, wine racks, chaise lounges and chair frames, shutters, and bed frames. Foaming agents are also used in the manufacture of automotive parts such as battery cases, fan covers, doors for small items, duct structures for air conditioners, upholstery materials, cushioning materials, bucket seat frames, and automotive sealants. .. Foaming agents are also used in plastic materials for making marine components such as boat ladders, center deck of sailboats, buoys and floats, modular hulls, lobster pots. Furthermore, foaming agents include pallets, trays, soda cases, tool boxes, drums and various containers,
Manufactures ice buckets, bird baths, croquet wood and balls, children's toys, recreational vehicle parts, bowling pins, shuffleboard equipment, sports equipment such as hockey sticks and baseball bats, and footwear. Used for plastic material. Further, foaming agents are used with adhesive plastic materials in hot melt adhesives. The foaming agent is also used as a food packaging material to be attached to the outside of livestock after slaughtering the livestock and before wholesale. Such products are sometimes called "bone wraps".

Generally, the chemical blowing agent is mixed with a solid plastic material and then the mixture is heated under pressure. The heating causes the plastic material to fluidize and the foaming agent releases gas. This gas forms bubbles or microchambers in the fluid plastic material. The mixture is placed under pressure in a mold where the gas expands and the fluid plastic material expands. The microchamber structure remains intact after solidification. Since the gas release temperature varies depending on the type of foaming agent, the foaming agent is selected according to the processing conditions, the plastic material, and the desired bubble size.

[0005]

[Problems to be Solved by the Invention] Chemical blowing agents include
It has the advantage over gaseous blowing agents that it can be added to the solid plastic material before heating. Gaseous blowing agents such as nitrogen and some fluorocarbons must be injected into the fluidized plastic material. In hot melt adhesives, gas is mixed into the adhesive before the end of the nozzle. The use of fluorocarbons as blowing agents has come under close scrutiny because their impact on the Earth's ozone layer has become a problem. Other conventional foaming agents have handling, toxicity and flammability issues. Handling problems include storage stability, dust, and risk of explosion.

[0006]

It has now been found that a complex of cyclodextrin and a foaming agent acts as a foaming agent in a fluidized plastic material. Cyclodextrins have been found to stabilize foaming agents. It was also found that certain compounds, which have never been used as foaming agents, can be used as foaming agents.

The present invention comprises the steps of forming a mixture of a plastic material and a complex of a blowing agent and cyclodextrin, and heating the mixture to fluidize the plastic material and release gas into the composite. And a method of expanding a plastic material. The gas forms bubbles in the fluidized plastic material.

First, a complex of cyclodextrin and a foaming agent is formed, and the complex is mixed with a plastic material.

The step of heating the mixture is carried out by applying heat to the mixture as is generally done by conventional extrusion or blow molding methods, or by the heat of exothermic reaction normally carried out in the case of polyurethanes.

The inflatable plastic composition produced according to the present invention comprises a plastic material and a complex of cyclodextrin and a blowing agent. Inflatable plastic compositions are used, for example, to make foam structures and certain adhesives.

The expanded structure formed according to the present invention is
It is prepared by heating and molding a mixture of a structural plastic material and a complex of a blowing agent and cyclodextrin.

The adhesive and / or sealant composition produced according to the present invention comprises an adhesive and / or sealant plastic material and a complex of a foaming agent and cyclodextrin.

Cyclodextrin, also called "Schalzinger dextrin", cycloamylose, cyclomaltose and cycloglucan, is an oligomer of anhydroglucose which is linked together by alpha 1,4 bonds to form cyclic compounds. 6-membered ring is alpha cyclodextrin, 7-membered ring is beta cyclodextrin,
And the 8-membered ring is called gamma cyclodextrin.
These 6, 7 and 8 membered rings are also referred to as cyclomaltohexaose, cyclomaltoheptaose and cyclomaltooctaose, respectively.

Cyclodextrin is usually obtained by treating a starch slurry with an enzyme or an acid to give a gelatinized, liquefied slurry having a DE between 1 and 5. The gelatinized, liquefied starch slurry is then treated with cyclodextrin glycosyl transferase (CGT) to a pH suitable for the selected CGT,
Treat at temperature and time. The enzyme CGT is Bacillus
Cerance , B. Magatherium , B. Circulance ,
B. Stearothermophilus, and Bacillus sp.
(Alkalophilic), obtained from other microorganisms. Then, the gelatinized and liquefied starch slurry is treated with CGT to separate and purify the digested product, whereby cyclodextrin is obtained.

One of the commercially important characteristics of cyclodextrins is their ability to act as clathrates or hosts for other commercially available compounds. Cyclodextrins physically have a donut shape. As a result, cyclodextrins can act as clathrates for substances that have a geometric outer dimension that corresponds to the diameter of the cyclodextrin space. The cyclodextrin is often modified like a hydroxypropyl cyclodextrin by adding a side chain to the donut-shaped exterior.
The term "cyclodextrin" as used herein and in the claims means not only cyclodextrin itself, but also modified cyclodextrin and branched cyclodextrins.

As used herein and in the claims, the term "complex" or the expression "complex of cyclodextrin and a blowing agent" is such that cyclodextrin acts as a host on the blowing agent. It means not only a composition of cyclodextrin and a foaming agent, but also a composition in which the foaming agent is bound to the outside of cyclodextrin by a weak binding force.

As a method of forming a complex of cyclodextrin and a foaming agent, there is a method of dissolving cyclodextrin in water together with the foaming agent and collecting the resulting precipitate.

Another method is to load a ball mill with cyclodextrin and a foaming agent and grind the mixture in the hole mill for a certain period of time to form a complex between the cyclodextrin and the foaming agent. Other known methods for forming a complex between cyclodextrin and a foaming agent include kneading, lyophilization, and co-milling. Good results have been obtained with co-milling using a mortar and pestle.

Preference is given to using alpha, beta or gamma cyclodextrins for the present invention. Beta-cyclodextrin is preferred as it is commercially available. The conjugate prepared from the combination of all three cyclodextrins releases the foaming agent at different rates. It is considered that this is partly because the binding strength with the foaming agent differs depending on the cyclodextrin.

Suitable blowing agents include water, liquids such as propylene glycol, dipropylene glycol, tripropylene glycol, cyclohexylamine, dicyclohexylamine and ethylene glycol, and benzoyl peroxide and other peroxides which are difficult to process. There is a solid like a thing. It was surprising and unexpected that water, propylene glycol, dipropylene glycol, tripropylene glycol and ethylene glycol were effective as foaming agents. So far, water, propylene glycol, dipropylene glycol, tripropylene glycol and ethylene glycol have not been used as foaming agents because of their poor dispersibility in plastic materials. Solids such as benzoyl peroxide are
Processing is difficult due to the low decomposition temperature. Water and propylene glycol are considered safe and non-toxic to humans. Many conventional foaming agents are toxic to humans. The use of such a non-toxic foaming agent in the workplace brings unprecedented safety to the workplace. The use temperature of the foaming agent can be changed by using a combination of two or more foaming agents such as water and propylene glycol, or by using the same foaming agent with different cyclodextrins. ..

Further, according to the present invention, a hydrazine derivative which forms a complex with cyclodextrin, trihydrazide triazine, 5-phenyltetrazole, p-toluenesulfonyl semicarbazide, modified azodicarbonamide, and azodicarbonamide are used as a foaming agent. can do. Dust is reduced by complexing conventional foaming agent with cyclodextrin,
The composition stabilizes.

The amount of the foaming agent complexed with cyclodextrin is about 1 to about 30 parts by weight (phc) based on 100 parts by weight of cyclodextrin. More preferably about 3 to about
Complexed with cyclodextrin at 15 phc, most preferably about 5 to about 7 phc of the foaming agent.

When forming the complex between the cyclodextrin and the foaming agent, an excess amount of the foaming agent is used to form the complex.

Cyclodextrin obtained from commercial production of cyclodextrin has been found to be a suitable source of the complex of cyclodextrin and water. Cyclodextrins obtained from commercial production processes are generally about 10 to about
Contains 12 phc of water. When this cyclodextrin is used in an adhesive composition, sufficient gas is obtained by heating, so that commercially available cyclodextrin complexed with about 10 to about 12 phc of water acts as a foaming agent.

It has been found that, in general, the smaller the particle size of the composite, the more uniform the cell size. Good results have been obtained with a complex of cyclodextrin and foaming agent with a particle size that can pass through 200 mesh.

Suitable plastic materials include polymers such as polystyrene, polyvinyl chloride, polyethylene, polyurethane, polyphenols, polypropylene, polyisoprene (rubber), polybutadiene, as well as acrylonitrile-butadiene-styrene, styrene-isoprene, ethylene-. Butylene, styrene-butadiene rubber,
And copolymers such as ethylene vinyl acetate.

The foamed structure has a structure-like plastic material and about 1 to 100 parts by weight of the plastic material.
Produced by forming a mixture of about 15 parts by weight (php) cyclodextrin and water complex, heating the mixture to expand the plastic material, and allowing the expanded mixture to cool. More specifically, the foamed structure is made by conventional methods by placing about 1 to about 10 php of cyclodextrin and water complex together with the structural plastic material into the extruder hopper. The composite of the present invention is mixed with a plastic material, then the mixture is subjected to conventional molding steps, the mixture is heated and the fluidized plastic material is filled into a mold. Such molding operations are conventional. In the molding process, the conventional chemical blowing agent is replaced by the composite of the present invention.

Examples of structural plastic materials are polystyrene, polyethylene, polyurethane, polyisoprene, epoxy resins, and polyvinyl chloride.

The adhesive and / or sealant composition produced in accordance with the present invention comprises an adhesive plastic material and a complex of about 1 to about 30 php cyclodextrin and water.

Examples of adhesive plastic materials are ethylene vinyl acetate (EVA), acrylonitrile-butadiene-styrene and styrene-isoprene.
Good results have been obtained by using the conjugates of the invention and EVA.

The expandable plastic composition according to the present invention comprises about 1 to about 15 php of a foaming agent / cyclodextrin complex, and a plastic material. The expandable plastic composition is prepared by mixing the composite with a plastic material. A typical adhesive produced according to the present invention has the following composition. Parts by weight EVA 25-50 modified resin 25-60 wax 0-30 total amount of adhesive plastic material 100 antioxidant 0.05-0.5 php filler 0-100 php foaming agent-cyclodextrin complex 1-10 php The bookbinding adhesive produced according to the present invention has the following composition. Parts by weight EVA 35-45 modified resin 20-30 plasticizer 20-30 wax 10-20 total amount of adhesive plastic material 100 antioxidant 0.05-0.25 php foaming agent-cyclodextrin complex 1-10 php Antifungal agent (optional) 1-10 php Preferably, the blowing agent-cyclodextrin complex is a water-cyclodextrin complex and comprises about 8 to about 15 phc water. More preferably, the amount of composite used in the bookbinding adhesive is from about 3 to about 7 phc and contains from about 10 to about 15 phc water. When a bactericidal agent or antifungal agent is complexed with cyclodextrin and compounded in an adhesive to be used, it helps prevent deterioration. Water acts as a foaming agent and helps release fungicides or fungicides.

The bookbinding adhesive is produced by mixing all the components in a conventional manner.

The temperature of use of such adhesives is about 120 to about 20.
It is 5 ° C.

The use of the cyclodextrin / water complex offers several advantages over the prior art use of liquid nitrogen. Current machines for applying hot melts for bookbinding require specialized machinery for compounding liquid nitrogen. A much wider range of devices can be used with the cyclodextrin-water complex according to the invention. In addition, there is more open time, more surface contact, and less adhesive used to cover the same area.

The paper box and case sealing adhesive produced according to the present invention has the following composition: Parts by weight EVA 40 modified resin 40 wax 20 total amount of adhesive plastic material 100 antioxidant 0.01 php foaming agent-cyclodextrin complex 1-10 php Preferably, foaming agent-cyclodextrin complex is propylene glycol- It is a cyclodextrin complex and has about 8 to about 15 phc propylene glycol.
Preferably, the propylene glycol content is about 10 to about
Use about 3 to about 7 php of complex which is 13 phc.

Paper box and case sealing adhesives are prepared by mixing all the ingredients in a conventional manner.

The temperature of use of such adhesives is about 175 to about 20.
It is 5 ° C.

The carpet backing adhesive produced according to the present invention has the following composition. Parts by weight EVA 25-50 modified resin 25-60 wax 0-30 total amount of adhesive plastic material 100 antioxidant 0.05-0.5 php filler 0-100 php foaming agent-cyclodextrin complex 1-10 php The blowing agent-cyclodextrin complex used in this carpet backing adhesive is cyclodextrin and about 8 to about 15 phc water, propylene glycol, or a combination of water and propylene glycol, or water, propylene glycol. And a combination of hydrazine derivatives.

Further, such a carpet backing adhesive comprises a composite of cyclodextrin and a fungicide at about 1 p.
It is preferably included in an amount up to hp. Suitable fungicides include
There are diiodomethyl-p-tolylsulfone, phenol and butylhydroxytoluene, but diiodomethyl-p-tolylsulfone is preferred and its release is caused by the water released by the cyclodextrin.

The carpet backing adhesive is prepared by mixing all the ingredients in a conventional manner.

The operating temperature of the carpet backing adhesive is from about 149 ° C to about 177 ° C.

A small amount of an enzyme called amylase added to the expandable plastic material according to the present invention acts as a catalyst by heating, and enhances the rate at which the blowing agent is released from cyclodextrin. In order for the amylase to act as a catalyst, a small amount of water must be present in the plastic composition. It is believed that the amylase uses water to destroy the cyclodextrin, thereby promoting the release of the foaming agent.

Of course, other compounds can be added to the plasticizer material containing the foaming agent of the present invention, including fungicides, fungicides and perfumes.

These and other features of the invention are described in further detail by the examples provided below.

[0045]

EXAMPLE 1 This example illustrates a hot melt adhesive, particularly a bookbinding adhesive, according to the present invention. Binding material parts by weight EVA-507 45 Stavelite resin 25 Pentaline H 20 Microcrystalline wax 10 Total binding plastic material 100 This adhesive plasticizer material contains 0.1 php antioxidant and 10
The php water-beta cyclodextrin complex was added.
This complex contains 7.5 grams of beta-cyclodextrin and 2.5 grams of water. The cyclodextrin and water were complexed by mixing excess water with cyclodextrin. After mixing the adhesive plastics material with the antioxidant and the water-beta cyclodextrin complex, heating the mixture to 100 ° C causes water to transform from the liquid phase to the vapor phase at this temperature, thereby expanding the adhesive. Let The volume expansion coefficient of the adhesive was about 100%.

EVA-507 is an ethylene-vinyl acetate copolymer commercially available from Union Carbide. Stavelite resin is a hydrogenated resin and plasticizer containing diethylene glycol ester of hydrogenated resin, obtained from Hercules Powder Company. Pentaline H
Is a synthetic resin obtained from Hercules Powder Company. Microcrystalline wax is a commercially available wax obtained from Petrolite, Inc., Tulsa, OK. The antioxidant is Irganox 1010 obtained from Ciba-Geigy. Beta cyclodextrin is
Betacyclodextrin obtained from American Maze-Products, Inc. of Hammond, Indiana. The water is normal tap water.

It is surprising and unexpected that the complex of cyclodextrin and water in this formulation functioned as a foaming agent, as water itself does not function as a foaming agent in the binding adhesive. there were.

[0048]

Example 2 This example illustrates a method for producing an adhesive for paper boxes and cases according to the present invention. The following adhesive composition was prepared. Material parts by weight EVA-305 40 CKM-2400 15 Picolite A-115 12.5 Super Statak 12.5 Polywax 1000 10 Castor wax 10 Total adhesive plastic material 100 0.1 php antioxidant in this adhesive plasticizer material And 10
The propylene glycol-beta cyclodextrin complex of php was mixed. This complex contains 1 mol of beta cyclodextrin and 2 mol of propylene glycol. A complex of cyclodextrin and propylene glycol was prepared by mixing an excess of propylene glycol with beta cyclodextrin.

The mixture of adhesive material, antioxidant and propylene glycol-beta cyclodextrin complex was heated. Propylene glycol converted from the liquid phase to the gas phase, thereby expanding the adhesive composition. The adhesive composition contains propylene glycol, which is a foaming agent,
It expanded about 100% in volume.

EVA-305 is an ethylene-vinyl acetate copolymer commercially available from Union Carbide. CKM-2400 was obtained from Union Carbide. Picolite A-115 is a thermoplastic terpene resin obtained from Hercules. SuperStatac was obtained from Reihold Chemical Company. Poly wax 1
000 was obtained from Valeco and castor wax was obtained from Universal Pleasure Bachems. The antioxidant is Irganox 1010. Beta cyclodextrin is a beta cyclodextrin obtained from American Maze-Products, Inc. of Hammond, Indiana. Propylene glycol is a commercial product obtained from Dow Chemical Company.

Since propylene glycol itself does not function as a foaming agent, it was surprising and unexpected that the complex of cyclodextrin and propylene glycol in this formulation functioned as a foaming agent.

[0052]

EXAMPLE 3 This example illustrates the method of making the carpet backing adhesive of the present invention. The following adhesive composition was prepared. Material parts by weight EVA 50 Modified resin 40 Wax 10 Total of adhesive plastic material 100 Antifungal agent (optionally used) 1-10 php 0.1 php antioxidant, about 20 in this adhesive plasticizer material
The php filler and 5 php water-beta cyclodextrin complex were added along with 5 parts propylene glycol-beta cyclodextrin. The complex of this foaming agent and cyclodextrin was prepared as in Examples 1 and 2 above.
Was prepared according to. Both the foaming agent and cyclodextrin complex were simultaneously mixed with the adhesive composition in the same manner as in Examples 1 and 2.

Heating the mixture of adhesive composition and both blowing agents to about 195 ° C. caused the adhesive mixture to swell.

EVA is an ethylene-vinyl acetate copolymer. The modified resin is a commercially available wood rosin. Waxes are commercially available waxes commonly used in carpet backing adhesives. Antioxidant is Irganox 1010
And the filler is normal calcium carbonate.

[0055]

EXAMPLE 4 This example illustrates a method of making the pressure sensitive adhesive of the present invention.

The following adhesive composition was prepared. Material parts by weight EVA 501 15 EVA 605 30 Stavelite ester 10 37 Abitol 18 Total plastic adhesive 100 To this adhesive plasticizer material, 0.1 php of antioxidant Irganox 1010, 5 php of water and beta cyclodextrin complex, and 5 php cyclohexylamine and beta cyclodextrin were added. This water-beta-cyclodextrin complex contains 12.8 phc of water. A complex of beta cyclodextrin and cyclohexylamine, a volatile corrosion inhibitor, contains 8 phc of cyclohexylamine complexed with cyclodextrin.
Preparation of the composite and mixing of the adhesive composition were carried out as in Example 1.

The released moisture becomes a "trigger" mechanism,
This partially releases the complexed cyclohexylamine and equilibrates with the moisture released from the water-cyclodextrin complex. With such a mechanism, an effect of preventing corrosion on the metal surface can be obtained. Cyclodextrin stabilizes cyclohexylamine in the heating step by complexing with cyclohexylamine. Uncomplexed cyclohexylamine is unstable during the heating process of the adhesive. EVA501 and EVA605 are commercial ethylene-vinyl acetate copolymers obtained from Union Carbide. Stay Bright Ester 10
And Abitol was obtained from Hercules. The operating temperature of this adhesive is about 149-163 ° C.

[0058]

EXAMPLE 5 This example illustrates a method of making an inflatable and curable sealant according to the present invention.

A. - hot melt base material part Kraton FC1901x 100 (available from Shell) Regarurezu 1018 270 (available from Hercules) ene DEX 155 50 (available from Hercules) Irganox 1010 1 (available from Ciba-Geigy) B. -Plasticizer Overbased calcium sulphonate 10 (available from Witco) Beta-cyclodextrin: cyclohexylamine 2 complex (2: 1 molar ratio) Aluminum paste (available from Sun Oil 1 50:50 aluminum in Sunpearl 2280) ) Betacyclodextrin (10-13% HO) 2 Mix equal amounts of hot melt base and plasticizer, cool,
It was mounted on a cold rolled steel sheet or a galvanized cold rolled steel sheet. Place these sheets in a furnace at 200 ° C
Heated for 15 minutes. The material expanded on the plate both vertically and horizontally, doubling the volume.

[0060]

Example 6 50 parts of the hot melt base of Example 5 above
Part of overbased calcium sulfonate.
The overbased calcium sulfonate is heated to evaporate the water before mixing with the hot melt base. The mixture was placed on a cold rolled steel sheet and a galvanized cold rolled steel sheet and heated in a furnace at 200 ° C for 15 minutes. The mixture melted on heating and spread over the plate without expanding.

[0061]

Example 7 A mixture was prepared in the same manner as in Example 6 above, except that water was not evaporated from the overbased calcium sulfonate before mixing, and the cold-rolled steel sheet and the galvanized cold-rolled steel sheet were prepared. It was placed on top and heated in a furnace at 200 ° C. The mixture of this example was simply cured as it was. There is no fluidity or deformation of the material placed on the sheet.
As is apparent from the above, the curing was accelerated by the release of water.

[0062]

Example 8 A mixture was prepared in the same manner as in Example 5 above, except that the mixture was not cooled, placed on a cold-rolled steel sheet and a galvanized cold-rolled steel sheet, and heated at 200 ° C. in a furnace. Heated at. The material expanded in volume about twice. The blowing agent, water, was in the cyclodextrin and was released on heating along with the vapor phase corrosion inhibitor cyclohexylamine. The water is retained in the cyclodextrin and is not used for curing until sufficient heat is applied to cause its release.

[0063]

Example 9 A conventional sealant having the following composition was prepared. Materials - (available from Shell) Formula A part Kraton RD6501 100 Regarurezu 1018 270 (available from Hercules) ene DEX 155 50 (available from Hercules) Irganox 1010 1 (available from Ciba-Geigy) was mixed with this material, cold It was placed on hot rolled steel sheet and galvanized cold rolled steel sheet and heated in a furnace at 200 ° C. for 15 minutes. The mixture was melted by heating and spread on the plate.

[0064]

Example 10 This example uses Formulation A to prepare a sealant according to the present invention. Material Part Blend A 10 beta cyclodextrin (10-13% water) 2 Mix these materials and place them on a cold rolled steel sheet or a galvanized cold rolled steel sheet at 200 ° C. in a furnace.
Heated for 15 minutes. The mixture swelled, but not 100% of its original volume.

[0065]

Example 11 This example illustrates the use of another chemical blowing agent complexed with cyclodextrin. Material Part Blend A 10 beta cyclodextrin dibutyltin 2 dilaurate ester complex (24% chemical blowing agent) beta cyclodextrin (10 to 13% water) 2 After mixing, cold rolled steel sheet or zinc plating of these materials Cold rolled steel sheet and placed in a furnace at 200 ° C
Heated for 15 minutes. The mixture also expanded on heating to about 100% of its original volume.

[0066]

Example 12 This example illustrates the use of a complex of beta-cyclodextrin and benzoyl peroxide which acts as both a blowing agent and a curing agent for thermoplastics. The following compositions were prepared.

[0067] amount of material A. Fusabond C-D198 10 g (obtained from DuPont) Betacyclodextrin 1 g complex of benzoyl peroxide (10% benzoyl peroxide) B.I. Fusabond C-D198 10 g C.I. Fusabond C-D198 10 g beta cyclodextrin (10% water) 1 g D.I. Fusabond C-D198 10 g Benzoyl peroxide 0.1 g Each composition was mixed with heating and extruded into a sheet of uniform thickness between the liquids. A piece of equal length and weight was cut from this sheet, placed in an oven and heated at 200 ° C.

It was confirmed by the formation of bubbles that the uncomplexed benzoyl peroxide decomposed during mixing.

This was not confirmed when the complex of benzoyl peroxide and beta cyclodextrin was mixed under the same conditions. Both compositions had equal amounts of benzoyl peroxide. In the complexed state, benzoyl peroxide was stable upon mixing. Further, it was difficult to uniformly disperse benzoyl peroxide which was not complexed during mixing. The beta cyclodextrin-benzoyl peroxide complex was easily mixed when the composition was mixed and dispersed evenly.

After heating, the difference was very significant. Composition D, which contains uncomplexed benzoyl peroxide,
It set very quickly and did not spread widely. The bubbles in the cured composition were non-uniform in size and dispersion.

Composition A, which contained the beta-cyclodextrin complex of benzoyl peroxide, also cured rapidly and did not spread widely. Effervescence and hardening occurred simultaneously. This composition lifted higher than sample D with uncomplexed benzoyl peroxide. The bubbles of composition A were uniform in size and dispersion.

Composition C diffused better than any other composition. The water released from the cyclodextrin formed bubbles of uniform size and distribution. The water released acted as a conventional foaming agent, but there was no hardener to cure the composition and retard diffusion.

Composition B diffused more laterally than Compositions A and D, but not as much as Composition C. There was no diffusion retarding effector or diffusion enhancing foaming agent.

The best results were obtained with composition A containing a complex of benzoyl peroxide and beta cyclodextrin. Benzoyl peroxide was stabilized, released upon heating and acted as both a hardener and a foaming agent. The complex was easily mixed and dispersed in the composition.

Of course, all variations and modifications of the preferred embodiments of the invention described herein for purposes of illustration are included in the invention without departing from the spirit and scope of the invention.

The embodiments of the present invention will be described below item by item.

[0077]

Embodiment 1 A method for expanding a plastic material comprising forming a mixture of the plastic material and a complex of cyclodextrin and a foaming agent, and heating the mixture to form the plastic material. A method of fluidizing and expanding the plastic material with the foaming agent while the plastic material is in a fluidized state.

[0078]

[Embodiment 2] The method according to embodiment 1, wherein a step of forming a complex of the foaming agent and the cyclodextrin is carried out before forming the mixture.

[0079]

Embodiment 3 The method according to embodiment 1, characterized in that the heating step is achieved by mixing the plastic material, which causes an exothermic reaction in the plastic material.

[0080]

[Embodiment 4] The method according to Embodiment 1, wherein the heating step is performed by applying heat to the mixture.

[0081]

Embodiment 5 The plastic material is polystyrene, polyvinyl chloride, polyethylene, polyurethane, polybutadiene, polyphenol, polypropylene, polyisoprene, acrylonitrile-butadiene-styrene, styrene-isoprene, styrene-butadiene rubber, ethylene-butylene and ethylene-. A method according to embodiment 1, characterized in that it is selected from the group consisting of vinyl acetate.

[0082]

Embodiment 6 The method according to Embodiment 1, wherein the cyclodextrin is beta cyclodextrin.

[0083]

Embodiment 7 The foaming agent is one or more components selected from the group consisting of water, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol, cyclohexylamine, dicyclohexylamine and peroxide. The method of claim 1 characterized.

[0084]

Embodiment 8 The method of embodiment 1 wherein about 1 to about 15 parts by weight of said composite is mixed with said plastic material per 100 parts by weight of said plastic material.

[0085]

Embodiment 9 The method according to Embodiment 2, wherein about 1 to about 30 parts by weight of the foaming agent is complexed with the cyclodextrin per 100 parts by weight of the cyclodextrin.

[0086]

Embodiment 10 An inflatable plastic composition comprising a plastic material and a complex of cyclodextrin and a foaming agent.

[0087]

Embodiment 11 The foaming agent is one or more components selected from the group consisting of water, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol, cyclohexylamine, dicyclohexylamine and peroxide. The inflatable plastic composition of claim 10, characterized in that

[0088]

Embodiment 12 The plastic material is polystyrene,
Characterized by being selected from the group consisting of polyvinyl chloride, polyethylene, polyurethane, polybutadiene, polyphenols, polypropylene, polyisoprene, acrylonitrile-butadiene-styrene, styrene-isoprene, styrene-butadiene rubber, ethylene-butylene and ethylene-vinyl acetate. The inflatable plastic composition according to embodiment 10.

[0089]

Embodiment 13 The inflatable plastic composition according to embodiment 10, wherein the cyclodextrin is beta cyclodextrin.

[0090]

[Embodiment 14] Embodiment 10 characterized in that, based on 100 parts by weight of said cyclodextrin, about 1 to about 30 parts by weight of a foaming agent is complexed with said cyclodextrin.
The inflatable plastic composition described.

[0091]

Embodiment 15 The inflatable plastic composition according to embodiment 10, wherein the amount of the composite in the composition is about 1 to about 15 parts by weight based on 100 parts by weight of the plastic material. object.

[0092]

Embodiment 16 An adhesive and / or sealant composition comprising an adhesive material and a complex of cyclodextrin and a foaming agent.

[0093]

Embodiment 17 The adhesive plastic material is ethylene-
An embodiment, which is a copolymer of vinyl acetate, wherein the foaming agent is one or more components selected from the group consisting of water, propylene glycol, dipropylene glycol, tripropylene glycol and ethylene glycol. 16. The adhesive described in 16.

[0094]

Embodiment 18 The adhesive according to embodiment 16, wherein the composite is present in the adhesive in an amount of about 1 to about 10 parts by weight per 100 parts by weight of the adhesive plastic material. ..

[0095]

Embodiment 19 The adhesive according to embodiment 16, wherein the foaming agent is present in the complex in an amount of about 3 to about 30 parts by weight per 100 parts by weight of cyclodextrin.

Claims (19)

[Claims] 1. A method for expanding a plastic material comprising forming a mixture of the plastic material and a complex of cyclodextrin and a foaming agent, and heating the mixture to form the plastic material. A method of fluidizing and expanding the plastic material with the foaming agent while the plastic material is in a fluidized state. 2. The method according to claim 1, wherein a step of forming a complex of the foaming agent and the cyclodextrin is carried out before forming the mixture. 3. A method according to claim 1, characterized in that the heating step is achieved by mixing the plastic material, thereby causing an exothermic reaction in the plastic material. 4. The method according to claim 1, wherein the heating step is performed by applying heat to the mixture. 5. The plastic material is polystyrene, polyvinyl chloride, polyethylene, polyurethane, polybutadiene, polyphenol, polypropylene, polyisoprene, acrylonitrile-butadiene-styrene, styrene-isoprene, styrene-butadiene rubber, ethylene-butylene and ethylene-. The method of claim 1, wherein the method is selected from the group consisting of vinyl acetate. 6. The method of claim 1, wherein the cyclodextrin is beta cyclodextrin. 7. The foaming agent is one or more components selected from the group consisting of water, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol, cyclohexylamine, dicyclohexylamine and peroxide. The method of claim 1 characterized. 8. The method of claim 1 wherein about 1 to about 15 parts by weight of said composite is mixed with said plastic material per 100 parts by weight of said plastic material. 9. The method of claim 2, wherein about 1 to about 30 parts by weight of the blowing agent is complexed with the cyclodextrin per 100 parts by weight of the cyclodextrin. 10. An expandable plastic composition comprising a plastic material and a complex of cyclodextrin and a foaming agent. 11. The foaming agent is one or more components selected from the group consisting of water, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol, cyclohexylamine, dicyclohexylamine and peroxide. 11. The inflatable plastic composition according to claim 10, characterized in that 12. The plastic material is polystyrene,
Characterized by being selected from the group consisting of polyvinyl chloride, polyethylene, polyurethane, polybutadiene, polyphenols, polypropylene, polyisoprene, acrylonitrile-butadiene-styrene, styrene-isoprene, styrene-butadiene rubber, ethylene-butylene and ethylene-vinyl acetate. The inflatable plastic composition according to claim 10. 13. The inflatable plastic composition according to claim 10, wherein the cyclodextrin is beta cyclodextrin. 14. The inflatable plastic according to claim 10, wherein about 1 to about 30 parts by weight of the foaming agent is complexed with the cyclodextrin per 100 parts by weight of the cyclodextrin. Composition. 15. The inflatable plastic composition of claim 10, wherein the amount of the composite in the composition is about 1 to about 15 parts by weight based on 100 parts by weight of the plastic material. object. 16. An adhesive and / or sealant composition comprising an adhesive material and a complex of cyclodextrin and a foaming agent. 17. The adhesive plastic material is ethylene-
A copolymer of vinyl acetate, wherein the foaming agent is one or more components selected from the group consisting of water, propylene glycol, dipropylene glycol, tripropylene glycol and ethylene glycol. 16. The adhesive described in 16. 18. The adhesive of claim 16, wherein the composite is present in the adhesive in an amount of about 1 to about 10 parts by weight per 100 parts by weight of the adhesive plastic material. .. 19. The adhesive of claim 16, wherein the foaming agent is present in the composite in an amount of about 3 to about 30 parts by weight per 100 parts by weight of cyclodextrin.